Photographic developer



2,264,550 rnorocnnrmo nnvELor-sa Joseph B. Dickey and James G. McNally,Rochester, N. Y., asslgnors to Eastman Kodak Company, Rochester, N. Y.,a corporation oi New Jersey No wing. Application November 6, lull",

m Serial No. 413,041

'3 Claims.

7 This invention relates to amino compounds containing at least onefuryl or tetrahydroiuryl group; More particularly, this inventionrelates to arylamines containing one or more iuryl or tetrahydroiurylgroups which are useful for making the aforesaid compounds.

This application is a continuation-impart of our applications Ser. No.269,218, filed April 21,

119% (now ll. 8. Patent 2,273,564, dated February photogaphic purposes,and novel processes for 17, 1942), Ser. No. 298,086,-fi1ed October 5,1939 (now U. 8. Patent 2,292,212, dated August 4, i942) and Sex-"No.301,466, filed October 26,1939 (now abandoned). While our aminocompounds may be employed for a number of purposes industrially, we willdescribe their use in particular ior photographic purposes. Although anumber of compounds have been tested for photographic developers, manyof the prior art compounds do not give very fine-grain development, orsome of the compounds which do give fine-grain development, many exhibitadverse biological activity,

or. otherwise present disadvantages. It is, theretore, apparent that thedevelopment of new compounds and processes of producing the compoundswhich give improved results, as for example, flnegrain photographicdevelopment, is a highly desirable result.

This invention has for one object to provide new compounds containing atleast one furyl group-inthe' molecule. ,Still another object is toprovide new compounds, containing fury! groups in the molecule, whichare useful for photo-' graphic purposes. Still another object is toprovide novel phenylenediamine' compounds containing at ieast one furyl,tetrahydroiuryl, or the like group in the molecule which may be employedwith various alkalineand other materials for photographic developing.Stillanotherobject is to provide novel compounds containing a. furylgroup in the molecule, whichcompounds are use ml for line-grainphotographic development. Still another object is to'provide various newchemical compounds useful. as amines, or other wise in the preparationof 'theioregoing. Still another object is to providenovelprocesses whichmay beemployed for producing the aforementioned compounds. Other objectswill appear hereinafter;

We have found that certain new arylamine I compounds containing a groupsuch as a tetrahydrofuryl group, or other furyl group, may be prepared,certain of the compounds being useful j for photographicpurposes, as forexample, fine- -'as hydrogen, substituted or unsubstituted 1:

Z5! n R (D p) "n development. Certain oi our compounds may beexemplified by the iollo formula:

1 carbon chain) "{i ehydroiuryl In, regard to the iuryi group, forconvenience and brevity herein we employ this term to embrace thevarious to alpha, beta, or tetrahydroiuryl alpha and beta and the like.The

' various forms which the iuryl group may have are described in numeroustents in chemistry,

hence, it is unnecessary to so into detail herein except to indicatethat in general we prefer the group known as the a-tetrahydrofurylgroup. However, generically, our vention embraces the othermodifications, either the sple drogenated furyl groups, the b-iurylgroups, or combinations thereof. The mnemmr designated Z is a.substituent' such as amino, halogen, hydrorcy, alkoxy, allsyl, and thelike, as will be further apparent from the description which follows:

1!. is an integer 4 or less. R is avmember suc alkylene, aryl, cyclicaryl, or heterocyclic. An

example of a heterocyclic would be when'R comprised-(carbonchain)-.furyl. The carbon chain referred tov usually comprises a simplealkylene linkage, as will be observed from the example which follows. r

However, it'wili be noted that some of the hydrogens on the alkylenemember may be substituted in various ways. For convenience and brevity,however, we refel'to all of such groups as an alkylene group unless thecontext indicates otherwise.

We have found several novel methods by which our new compounds may beprepared. These methods are generically illustrated by the followingformulations which will be explained in detail as the descriptionproceeds.

i i a N OK 1 )N-(CHa) riuryl or tetrahydromryl "9) i I a l H iuryl orN-( CH1) tetrahydro-+ (H)catalytically' iuryl' chemically NO; (0, p)

il) I H HzN N-(CH:) liuryl or tetrahydroluryl N: (CHflriuryl ortetrahydroiuryl D) Reduce as in II Rz-N= 051). iuryl or tetrahydrolurylReduce as in II V m R HONO N CH1) iuryl or tetrahydroiuryl f") N O NCH1) rim] or tetrahydroluryl Reduce as in II Y %m R BNO: v

CH2) I iuryl or tetrahydroluryl N0: Z ;/R D) (3H iuryl ortetrahydrofuryl Reduce as in II VII (0, p) phenylenediamineH0(CH|),iuryl nickel catalyst at zoo-250, 10-24 hours m e 0 .I I H x EN--(CH;),iuryl or tetrahydroluryl I (0 5) VIII Z0) NQNH: H0 (CH1), 1 lor tetrahydroiuryl (ni el mtalyst as in VII) blocked NCN monoor dii'urylor tetrahydrofuryl choked) Then hydrolize.

Ix 2m a halo +b aoH tal O te ahydroiwyf 0) NOQN-R V cnlmur i ortetrahydroiuryl 'Then reduce as in 11 Referrin to the process I whereina furylamin'e is employed, such an amine would preferably be asaasooprepared by reacting th corresponding hydroxy furfuryl compound with anamination agent such as ammonia in the presence of a catalyst. Theformation of such iuryl amines will be apparent from the followingexamples:

Example 1 is then treated with a saturated aqueous solution of sodiumhydroxide, extracted with ether, dried over potassium hydroxide anddistilled. The tetrahydrofurfurylamine obtained is 12% of the theorybased on the alcohol charged into the bomb. The amine boiled at152-155/760 mm. Exactly similar results are obtained using a catalystsuch as that prepared from nickel nitrate through the hydroxide, to theoxide and then reduced. This material may be supported on pumice orsimilar material.

Example 2 Example 3 202 gms. tetrahydrofurfuryl alcohol, gms. anhydrousammonia and 10 gms. nickel or reduced nickel oxide are heated at 200-205for 34 hours and the reaction product is worked up as described inExample 1. There is obtained 34% tetrahydroiurfurylamine, 22%di-tetrahydrofurfurylamine and 6.2% tri-tetrahydrofurfurylamine, B. P.155-157/2 mm. This compound is a colorless, water-soluble liquid havingthe constants Nn1.4835/25; calcd. for C15Hz1NO3: C, 66.91; H, 10.03; N,5.20. Found: C, 67.39; H, 10.17; N, 5.40.

In place of nickel we may use a reduced nickel prepared by any process,which may be supported on material such as pumice, charcoal,diatomaceous earth, etc.

Example 4 gms. ditetrahydrofuri'urylamine, 100 gms. tetrahydrofurfurylalcohol and 5 gms, nickel are heated at 200-230 for 40 hours. Thereaction products are fractionated and there is obtained a. 20% yield oftritetrahydrofuriurylamine, a small amount of tar and a basicwater-insoluble material boiling at 110/2-mm.

Example 5 An aluminum oxide catalyst is prepared as follows: 200 gms. ofcrystalline aluminum nitrate are dissolved in 21. water and 200 gms.infusorial earth are added. Then ammonium hydroxide is added in a slightexcess. Wash thoroughly, dry the product .at room temperature andpulverize.

The catalyst thus prepared is placed in a Pyrex tube heated to 200-250'and the vapor of tetrahydrofurfuryl alcohol containing the desiredmolecular ratio of alcohol to ammonia is led over the catalyst at anydesired rate. For example, pass 0.8 of a mole of tetrahydrofurfurylalcohol containing 3 moles of ammonia per hour over 60 gms. of catalyst.The reaction products maybe recirculated if diortritetrahydroiurfurylamine are desired. On the basis of the alcoholreacted there is obtained a good yield of amines.

Example 6 Finely divided nickel oxide is made into a paste withcolloidal silica and the paste is deposited on pumice granules.

20 gms. of the catalyst are heated with 202 ms. of tetrahydrofurfurylalcohol and 70 gms. 01' ammonia at 220-230 for 36 hours. The reactionproducts are worked up as described in Example 1. The yields of primary,secondary, and tertiary amine are 36%, 30%, and respectively. It ahigher yield of primary amine is desired, more ammonia is used orsecondary amine is added.

This catalyst may be used to react with the alcohol or ammonia in thegas phase as described in Example 5 Example 7 A catalyst composed ofalumina supported on silica gel is prepared as follows: 300 gms. ofsilica gel are heated at 398-400 under reduced pressure for 4 hours andcooled. Then 135 gms. oi aluminum nitrate are dissolved in 650 cc. ofwater and the silica added. After standing for a few hours theimpregnated gel is filtered off and heated at 400.

The catalyst prepared as described i then placed in a suitable reactionvessel and tetrahydroiuriuryl alcohol in the vapor state containingammonia (molecular ratio 1:3 or 1:5) is passed over the catalyst heatedto 300. The conversion of alcohol to amine is about -25% for a contacttime of l 2 seconds The relative amounts of amines formed are primarysecondary 20%. tertiary 6%.

Similar results can :be obtained it active char coal is impregnated withaluminum or nickel nitrate and the precipitated hydroxide fused asabove.

- Example 8 440 gms. p-tetrahydrofurfuryloxyethanol, 130 gms. ammoniaand 10 'gms. nickel from anickei alloy were heated in a shakingautoclave at 210- 220 for hours. The reaction products were cooled andfractionated to give a 33% vyield of ptetrahydrofurfuryloxyethylamine,B. P.. 162-164/ 740 mm., 3% di p --tetrahydrofurfuryloxyethylamine, B.P. 220-225/19 mm. and a small amount of tri-3-tetrahydrofurfuryloxyethylamine, B. P. 274-2'79/ 18 mm. Most of thefurfuryl compound that did not react was recovered.

Example 9 4'40 gins p-tetrahydrofurfuryloxyethanol,- 120 gms. ammoniaand 8gms. nickel onkieselguhr (J. Amer. Chem. Soc. 54, 661-1932) wereheated in an autoclave with vigorous stirring at 200-230 for 24 hours.There was obtained a 25% yield of the monoamine.

- Example 10;

440 gms. p tetrahydrofurfuryloxyethanol,' 100 gms, ammonia, 5 gms.nickel from a nickel alloy and 5 mos. of a copper-chromium-zinc oxidecatalyst were heated in a shaking autoclave at 200- 250 ior,24 hours.There was obtained a good yieldotthcmonoamine.

I l 5 etc. catalyst 'H+CH: H--(C Ha) OH v 30 o l, 2, 3, or 4 I Example11 An aluminum oxide catalyst was prepared as follows: 200 gms. aluminumnitrate was dissolved 5 in 2 liters of water and 200 gms. infusorialearth was added. Then ammonium hydroxide ,was

added inslight excess- The product was washed well, dried at roomtemperature and pulverized. The catalyst thus prepared may besubstituted in the above operations or may be placed in a utilization ofa compound having the formula;

aryl-carbon chain-,iuryl which is reacted with 9. nitro medium such as vHONO or HNOa, these arylcompounds may be 25 prepared in several ways asfollows:

(2: Nickel- 0O poet UH -OH: ehromate Further details concerning theforegoing Reac- 'tions X-XIII can be observed fromthe following specificexamples:

' Emafmple 12 70- 5 I '200 gms.- of aniline, gms. of tetrahydroturfurylalcohol, and 5' gms. of nickel on'kieselguhr are heated in a shakingautoclave at 210- 220 for 30 hours, cooled, removed, and filtered.

7 5 On distillation there is obtained a good yield of CHr-CHs H I lN-(CHz) CH CH5 1,2, 3, or 4\ O t 4 N tetrahydrofurfurylaniline boilingat 1701'74/13 Example 13 200 gms. of m-toluidine, 150 gms. oftetrahydrofurfuryl alcohol, and 10 gms. of nickel are heated in ashaking autoclave for 40 hours at a temperature ranging between 200-250.n working up as before there is obtained a good yield oftetrahydrofurfuryl-m-toluidine, B. P. l'75-180/l4 mm. This on heatingwith butyl chloride or bromide gave a good yield ofbutyltetrahydrofurfuryl-m-toluidine boiling at 193- 195/ 22 mm.

' Example 14 200 gms. of o-anisidine, 100 gms. of fi-tetrahydrofurfurylethanol, and gins. of copper chromiterare heated as in Example 1. Ondistillationthere is obtained a good yield ofB-tetrahydrofurfuryl-o-anisidine, B. P. 186193/13 mm.

Example 15 123 gms. of furanacrolein (1 mole), 107 gms. (1 mole) ofo-toluidine, and 5 gms. of nickel are heated to 100. Then hydrogen undera pressure of 1500 lb. is introduced and when 4 moles of hydrogen havebeen taken up reduction is stopped and there is obtained a good yield of'y-tetr'ahydrofurylpropyl-o-toluidine boiling at 1801 85/13 mm.

Example 16 One mole of tetrahydrofuryl-m-toluidine is heated in anautoclave at 200 for 8 hours with 1 mole of ethylene oxide. Ondistillation there is obtained an excellent yield ofp-hydroxyethyltetrahydrofuryl-m-toluidine boiling at 152154/2 mm. Inplace of ethylene oxide, propylene, trimethylene, tetramethylene,glycidol and the like are used. If in place of one mole of ethyleneoxide above we use two or more we obtain p-hydroxy3-ethoxyethyltetrahydrofurfuryl-m-toluidine.fi-hydroxy-Ii-ethoxy-3-ethoxy-ethyltetrahydrofurfuryl-m-toluidine, andthe like may be prepared similarly.

Example 1,?

recovered. In place of. chloroacetamide we mayuse chloroacetic acid,ethylchloro acetate, ethyl ene imine, bromoalkyl sulfonates, sulfonatedbenzyl chloride, etc.

On referring to the process of'IV, the azo starting material or thisprocess may be obtained by procedure as follows:

' stricted to the exact catalyst indicated, but varions coppermaterialssuch as copper chromite or catalysts such as tungsten, molybdenum oroxides may be employed. When we employ the terms nickel catalyst,"copper catalyst and the like herein, we embrace not only the singlecomponent catalyst, but catalysts wherein there may be other componentsexemplified by nickel oxide, chromites, and other oxides or salts of thevarious catalyst materials herein described.

However, our process is not restricted to the use of catalyticreduction, but it is possible in many instances, particularly whereverthere is a furfurylidene linkage, to carry out the reductionelectrolytically. The furfurylidene compound would be reduced in anaqueous alcoholic solution of sodium acetate or other comparablematerials, acting as a combined electrolyte and solvent. These aqueouscomponents act as an electrolyte and the alcohol as a solvent. A leadcathode would preferably be employed. A relatively high temperature, asfor example 15 C. to under C. may be employed. The anode would comprise,for example, cylindrical sheet nickel. Various current densities andpotentials may be employed, as for example, V1 of an ampere per squarecentimeter and a potential of around 5 volts; However, other currentdensities up to, for example, .05 ampere per square centimeter andvoltages above 10 volts, may be employed. Or the metals such as zinc,aluminum, tin, cadmium, and mercury may be employed. Also, variouscompounds may be used as solvents in an electrolyte such as tertiaryamines, ammonical ammonium chloride, sulphonates, or even sodiumhydroxide may be added to the electrolyte.

The furyl product can be separated by evaporating or distilling off thealcohol which, of course, throws the compound out of solution.

It is believed apparent from the foregoing disclosure with respect tothe details of the compounds employed, as to how the preferredphenylenediamine compounds of our invention may be prepared by followingthe several procedures indicated under I-lX. However, further specificdetails respecting operation of our processes will be had from thefollowing examples:

Example 19 100 ms. or p-phenylenediamine, 20 gms. nickel, and 60 gms.tetrahydrofurfuryl alcohol are heated in a shaking autoclave at 220 for24 hours; the reaction product is fractionated'to charged intoanautoclave with 10 .gms. copper chromite and hydrogenated at 50-150 under2-200 atmospheres pressure. When 3 mo]. of hydrogen have been absorbed,the, reaction is stopped, cooled and distilled.

\ Example 21 Cu acetate Cu 01:

63.0 gms. (0.6 M) tetrahydroiurfurylamine 32.0 gms. (0.2 M)p-nitro-chlorobenzene 17.0 sms. (0.2 M) sodium bicarbonate Trace of Cupowder, CliC'lz, Cu acetate were charged into a 500 cc. 3-necked flaskwith ing solution to 15 minutes did not further increase NO: I

100 cc. of pyridine and heated to reflux for forty hours by means of adirect flame. The reaction mass was cooled to room temperature,filtered, and the filtrate washed with ether. The low boiling solventssuch as ether and'most of the 'pyr-' idine were removed by vacuumdistillation at taining a temperature of 65 C. at 16 m. 111. Weight ofresidue, 66 ms. The residue was steamv distilled to remove traces ofunreacted Sixty gmsof the crude product was dissolved in with methodsfor their preparation, and while these new compounds have a number ofuses, we

have found,as already indicated, that certain .of these compounds areparticularly useful for photographic purposes, and-the followingdescription respecting the advantages of our'compounds for such purposesis not to be considered a derogation of the use otthe compounds forother-purposes. for which their are suitable. Briefly. the methodemployed for..ph tograpliic determinations comprises preparing ournovelcompounds with well known standard developers. That'is. roll film wasexposed in .a certain manner and strips thereof developed in a mediumcomprising a developer of certainoflour new compounds, and

in the case of the standard the development com- .prised a knownstandard. Inasmuch as the agitation, exposure, and the like conditionswere kept the same for the tests the differences observed could .beconsidered as flowing from the use of our compounds being tested. 1Graininess was determined by microscopic examination at a low degree(approximately. 10 x 202).

- The various compounds tested were made up into various formulas.Fol-example, in some formulas 5 gms. of our novel furyi compound wasmixed with a substantial amount, as for example gm. of sodium suliltogether with a substantial content of es or other materials. That is,various other materials, such as sodium carbonate, alkali metalmetaborates, and bromide such as potassium bromide maybe incorporated.Briefly. some of the results obtained were as iioliows:

N (4 amino-.l-awthylphenyll -N-tetmhydroiurfli t! a anine-amide/CH1r-'CONHa cur-cm cnr-cn n, \o a This was a tan powderwhich. althoughsoluble in hot water, precipitated slowly from solution. The 30-minutedeveloper prepared with caustic soda gave moderately high speeds andgees,- which were out decidedly by small amounts of bromide. Increasingthe activity of the developthe graininess.

r rms This light gray powder was readily soluble in water and sulflte toproduce almost colorless,

I stable solutions. It was active in be alone and gave high emulsionspeed and a w-toncd image of moderate graininess. It was very sensi tiveto bromide and other silver halide reactants. Progressively increasingactivity, obtained with metaborate addition, decreased this sensitivityto bromide.

This white powder was quite methyl aminophenol sulfate. It was slightlyless active, yielding about the same emulsion speed, fog, andgraininess, and possessed a similar sensitivity to addition agents.

This agent was readily soluble in warm water to give a bright pinksolution which became colorless on the addition of sulflte. It wasstable for. sulflte concentrations up to 15 gmaper liter, but somewhatunstable. at 25 gms. per liter.- It was active, producing a warm tonedimage and slight- 6 1y high fog. The graininess was low in the activedevelopers, and both graininess and fog were cut by bromide. Emulsionspeeds, measured by gradient or threshold methods, were high, showihg ahighly efllcient developer. Y 'Iherefore, it can be seen from theforegoing is 2 aminc-S-ethill N-tetmhydrofcrmryl-p-cmlol aresimilartothehthat our compounds exhibit desirable properties and thatthey can be employed in various ways, as for example in variousadmixtures for photographic purposes. We have found that of ourcompounds, those having substituents on the aryl nucleus in someinstance improve the photographic properties.

It is also apparent from the foregoing that our invention contemplatesvarious modifications of our compounds and various methods of producingthe compounds, employing various catalysts, methods of reduction and thelike.

What we claim and desire to be secured by Letters Patent of the UnitedStates is:

1. A photographic developer which contains, as an essential ingredient,a substantial amount of an amino compound of the following generalformula:

HzN N alkylene-Fu wherein Fu represents a member selected from the groupconsisting of furyl groups and tetrahy-' drofuryl groups, R represents amember selected from the group consisting of hydrogen, alkyl groups,hydroxy alkyl groups, alkoxy alkyl groups,

. cycloalkyl groups, amidoalkyl groups, aryl groups alkylene- H H:

3. A photographic developer which contains, as

an essential ingredient, a substantial amount of an amino compound ofthe following formula:

4. A photographic developer which contains, as an essential ingredient,a. substantial amount of an amino compoundof the following formula:

C z a 5. A photographic developer which contains, as an essentialingredient, a substantial amount of an amino compound of the followingformula:

6. A photographic developer which contains, as an essential ingredient,a substantial amount of an amino compound of the following fonnula:

CHr-CONH: HQN N CHg-CH:

alkyleno- H H: C x A o 7. A photographic developer which contains, as anessential ingredient, a substantial amount of an amino compound of thefollowing formula:

JOSEPH'B, DICKEY. JAMES G. MCNALLY.

